KR20070039088A - 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane refrigerant compositions comprising functionalized organic compounds and uses thereof - Google Patents

Abstract

The present invention relates to 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane and at least one chlorocarbon, alcohol, ether, ester, N- (difluoromethyl A composition for use in refrigeration and air conditioning systems comprising) -N, N-dimethylamine, or mixtures thereof. In addition, the present invention provides 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane and at least one chlorocarbon, alcohol, ether, ester, N- (di A composition for use in refrigeration and air conditioning systems using centrifugal compressors comprising fluoromethyl) -N, N-dimethylamine, or mixtures thereof. The compositions of the present invention may be azeotropic or near-azeotropic and may be useful as a heat transfer fluid or in a method for producing cooling or heat.

Refrigerants, heat transfer fluid compositions, air conditioning systems, azeotropic mixtures, ultraviolet fluorescent dyes

Description

1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane refrigerant composition comprising functionalized organic compounds and uses thereof {1,1,1,2,2, 3,3,4,4-NONAFLUORO-4-METHOXYBUTANE REFRIGERANT COMPOSITIONS COMPRISING FUNCTIONALIZED ORGANIC COMPOUNDS AND USES THEREOF}

<Cross Reference of Related Application>

This application claims priority to US provisional application 60 / 584,785 (filed June 29, 2004).

The invention relates to 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane and chlorocarbons, alcohols, ethers, esters, N- (difluoromethyl) -N A composition for use in refrigeration and air conditioning systems comprising at least one of, N-dimethylamine, or mixtures thereof. In addition, the invention provides 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane and chlorocarbons, alcohols, ethers, esters, N- (difluoromethyl A composition for use in refrigeration and air conditioning systems using a centrifugal compressor comprising at least one of) -N, N-dimethylamine, or mixtures thereof. The compositions of the present invention may be azeotropic or near-azeotropic and may be useful as a heat transfer fluid or in a method for producing cooling or heat.

The refrigeration industry has been trying to find alternative refrigerants for ozone depleted chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out as a result of the Montreal Protocol over the past decades. The solution for most refrigerant manufacturers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. HFC-134a, the new most widely used HFC refrigerant at present, has no potential for ozone depletion and is therefore not affected by the current phase-out regulations of the Montreal Protocol.

In addition, environmental legislation could ultimately lead to global phase out of certain HFC refrigerants. Currently, the automotive industry is facing legislation on the possibility of global warming for refrigerants used in automotive air conditioning. Thus, there is an urgent need to find new refrigerants with reduced global warming potential for the automotive air conditioning market. If the legislation is more widely applied in the future, there will be a greater need for refrigerants that can be used in all areas of the refrigeration and air conditioning industry.

Currently proposed HFC-134a replacement refrigerants include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as CO ₂ or ammonia. Many of the replacements given above are toxic and / or flammable. Therefore, new alternatives are always being sought.

It is an object of the present invention to provide novel refrigerant compositions and heat transfer fluids that provide unique properties to meet the requirements of low or no ozone depletion potential and low global warming potential compared to current refrigerants.

<Overview of invention>

The invention is C ₄ H ₉ OCH ₃ and

N- (difluoromethyl) -N, N-dimethylamine,

Diisopropyl ether,

Dimethoxymethane,

Ethyl acetate,

Ethyl formate,

Methanol,

Methyl acetate,

Methyl formate,

tert-butyl methyl ether,

Trans-1,2-dichloroethylene, and

C ₄ F ₉ OC ₂ H ₅ and trans-1,2-dichloroethylene

A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of:

The invention further relates to the compositions listed above for use exclusively in refrigeration or air conditioning systems using centrifugal compressors, multistage or two-stage centrifugal compressors or single passage / single slab heat exchangers.

In addition, the present invention relates to azeotropic or near-azeotropic refrigerant compositions. These compositions are useful for refrigeration or air conditioning systems. Such compositions are also useful for refrigeration or air conditioning systems using centrifugal compressors.

In addition, the present invention relates to a method of cooling, heating, and heat transfer from a heat source to a heat sink using the composition of the present invention.

The refrigerant composition of the present invention comprises C ₄ F ₉ OCH ₃ and at least one of chlorocarbons, alcohols, ethers, esters, N- (difluoromethyl) -N, N-dimethylamine, or mixtures thereof.

Representative components of the compositions of the present invention such as chlorocarbons, alcohols, ethers, and esters are listed in Table 1 below.

The compounds listed in Table 1 are either commercially available or can be prepared by methods known in the art. C ₄ F ₉ OCH ₃ and C ₄ F ₉ OC ₂ H ₅ are both mixtures of isomers and commercially available as shown in Table 1.

The compositions of the present invention, which are mixtures, can be prepared by any convenient method of combining the desired amounts of the individual components. The preferred method is to weigh the desired amount of ingredients and then combine the ingredients in a suitable container. Agitation can be used if necessary.

The composition of the present invention has no or low ozone depletion potential and low global warming potential. For example, C ₄ F ₉ OCH ₃ has lower global warming potential than many HFC refrigerants currently used alone or in mixtures.

Refrigerant or heat transfer compositions of the invention are C ₄ F ₉ OCH ₃ and

N- (difluoromethyl) -N, N-dimethylamine,

Diisopropyl ether,

Dimethoxymethane,

Ethyl acetate,

Ethyl formate,

Methanol,

Methyl acetate,

Methyl formate,

tert-butyl methyl ether,

Trans-1,2-dichloroethylene, and

C ₄ F ₉ OC ₂ H ₅ and trans-1,2-dichloroethylene

It includes a composition comprising at least one compound selected from the group consisting of.

The refrigerant or heat transfer composition of the present invention may be an azeotropic or near-azeotropic composition. An azeotropic composition is a liquid mixture of two or more materials having a constant boiling point that can be above or below the boiling point of the individual components. Thus, azeotropic compositions will not result in a classification that can reduce the efficiency of the system in a refrigeration or air conditioning system during operation. In addition, azeotropic compositions will not be classified as they leak from refrigeration or air conditioning systems. If one component of the mixture is flammable, fractionation during leakage can result in flammable compositions inside or outside the system.

Near-azeotropic compositions (also commonly referred to as "similar azeotropic compositions") are substantially constant boiling liquid mixtures of two or more materials that behave substantially as a single material. One property of the near-azeotropic composition is that the vapor produced by the partial evaporation or distillation of the liquid has a composition that is substantially the same as the liquid that evaporates or distills it. That is, the mixture is distilled / refluxed without substantial composition change. Another property of the near-azeotropic composition is that the bubble point vapor pressure and dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, if 50% by weight of the composition is removed, for example, by evaporation or boiling, and then the difference in vapor pressure between the composition remaining after 50% by weight of the original composition is removed is less than about 10%, the composition may -It's public.

The azeotropic refrigerant compositions of the present invention are listed in Table 2 below.

Near-azeotropic refrigerant compositions and concentration ranges of the invention are listed in Table 3 below.

Additional compounds other than those listed in Table 1 may be added to the binary compositions of the present invention to form three or more compositions. For example, from about 10 wt% to about 70 wt% C ₄ F ₉ OCH ₃ , from about 5 wt% to about 60 wt% C ₄ F ₉ OC ₂ H ₅ and from about 25 wt% to about 80 wt% Near-azeotropic compositions comprising trans-1,2-dichloroethylene can be formed at 50 ° C. (see last row of Table 3).

The composition of the present invention may further comprise from about 0.01% to about 5% by weight stabilizer, free radical scavenger or antioxidant. Such additives include, but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.

The composition of the present invention may further comprise from about 0.01% to about 5% by weight water scavenger (dry compound). Such water scavengers may include ortho esters such as trimethylortho formate, triethylortho formate, or tripropylortho formate.

The composition of the present invention may further comprise an ultraviolet (UV) dye and optionally a solubilizer. UV dyes are useful components for detecting leakage of refrigerant and heat transfer fluid compositions by allowing fluorescence of the dye in the refrigerant or heat transfer fluid composition to be observed at the point of leakage or in the vicinity of the refrigeration or air conditioning device. Fluorescence of the dye can be observed under ultraviolet light. Solubilizers may be needed to increase the solubility of UV dyes in some refrigerants and heat transfer fluids.

By "ultraviolet" dye is meant a UV fluorescent composition which absorbs light in the ultraviolet or "near-ultraviolet" region of the electromagnetic spectrum. Fluorescence generated by UV fluorescent dyes can be detected under illumination by UV light emitting waves having a wavelength between 10 nanometers and 750 nanometers. Thus, if a refrigerant or heat transfer fluid containing such UV fluorescent dye leaks from a particular point of the refrigeration or air conditioning apparatus, fluorescence can be detected at this point of leakage. Such UV fluorescent dyes include, but are not limited to, naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives or combinations thereof It is not limited. Solubilizers of the invention are from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes At least one compound selected.

Hydrocarbon solubilizers of the present invention include hydrocarbons, including straight, branched or cyclic alkanes or alkenes containing up to 16 carbon atoms and containing only hydrogen without other functional groups. Representative hydrocarbon solubilizers include propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, octane, decane, and hexadecane.

Hydrocarbon ether solubilizers of the present invention include ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).

Polyoxyalkylene glycol ether solubilizers of the invention are represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y where x is an integer from 1 to 3, y is an integer from 1 to 4, and R ¹ is Hydrogen and an aliphatic hydrocarbon radical having 1 to 6 carbon atoms and having y bonding sites, R ² is selected from aliphatic hydrocarbylene radicals having 2 to 4 carbon atoms, R ³ is hydrogen, and 1 to carbon atoms Is selected from six aliphatic and alicyclic hydrocarbon radicals, at least one of R ¹ and R ³ is selected from the hydrocarbon radicals, and the molecular weight of the polyoxyalkylene glycol ether is from about 100 to about 300 atomic mass units. As used herein, a bonding site means a radical site available for forming covalent bonds with other radicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals.

In the present invention, preferred polyoxyalkylene glycol ether solubilizers are represented by R ¹ [(OR ² ) _x OR ³ ] _y where x is preferably 1 to 2, y is preferably 1 and R ¹ And R ³ is preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, and R ² is preferably from aliphatic hydrocarbylene radicals having 2 or 3 carbon atoms, most preferably 3 carbon atoms. And the molecular weight of the polyoxyalkylene glycol ether is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. R ¹ and R ³ hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R ¹ and R ³ hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl Include. R ¹ and R ³ are preferred when the free hydroxyl radicals on the polyoxyalkylene glycol ether solubilizers of the present invention may be incompatible with certain compression refrigeration unit construction materials (eg, Mylar®). Preferably an aliphatic hydrocarbon radical having 1 to 4 carbon atoms, most preferably 1 carbon atom. R ² aliphatic hydrocarbylene radicals having 2 to 4 carbon atoms form repeating oxyalkylene radicals-(OR ² ) _x -including oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. In one polyoxyalkylene glycol ether solubilizer molecule, the oxyalkylene radicals comprising R ² may be the same, or one molecule may contain different R ² oxyalkylene groups. The polyoxyalkylene glycol ether solubilizer of the present invention preferably comprises one or more oxypropylene radicals. When R ¹ is an aliphatic or cycloaliphatic hydrocarbon radical having 1 to 6 carbon atoms and having y bonding sites, the radical may be linear, branched or cyclic. Representative R ¹ aliphatic hydrocarbon radicals having two binding sites include, for example, ethylene radicals, propylene radicals, butylene radicals, pentylene radicals, hexylene radicals, cyclopentylene radicals and cyclohexylene radicals. Representative R ¹ aliphatic hydrocarbon radicals having 3 or 4 binding sites include trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane. Residues derived by removing their hydroxyl radicals from polyalcohols.

Representative polyoxyalkylene glycol ether solubilizers are CH ₃ OCH ₂ CH (CH ₃ ) O (H or CH ₃ ) (propylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₂ (H or CH ₃ ) (dipropylene glycol methyl (or dimethyl) ether), CH ₃ O [CH ₂ CH (CH ₃ ) O] ₃ (H or CH ₃ ) (tripropylene glycol methyl (or dimethyl) ether) , C ₂ H ₅ OCH ₂ CH (CH ₃ ) O (H or C ₂ H ₅ ) (propylene glycol ethyl (or diethyl) ether), C ₂ H ₅ O [CH ₂ CH (CH ₃ ) O] ₂ ( H or C ₂ H ₅ ) (dipropylene glycol ethyl (or diethyl) ether), C ₂ H ₅ O [CH ₂ CH (CH ₃ ) O] ₃ (H or C ₂ H ₅ ) (tripropylene glycol ethyl ( Or diethyl) ether), C ₃ H ₇ OCH ₂ CH (CH ₃ ) O (H or C ₃ H ₇ ) (propylene glycol n-propyl (or di-n-propyl) ether), C ₃ H ₇ O [ CH ₂ CH (CH ₃ ) O] ₂ (H or C ₃ H ₇ ) (dipropylene glycol n-propyl (or di-n-propyl) ether), C ₃ H ₇ O [CH ₂ CH (CH ₃ ) O ] ₃ (H or C ₃ H ₇ ) (Tripropylene glycol n-propyl (or di-n-propyl) ether), C ₄ H ₉ OCH ₂ CH (CH ₃ ) OH (propylene glycol n-butyl ether), C ₄ H ₉ O [CH ₂ CH ( CH ₃ ) O] ₂ (H or C ₄ H ₉ ) (dipropylene glycol n-butyl (or di-n-butyl) ether), C ₄ H ₉ O [CH ₂ CH (CH ₃ ) O] ₃ (H Or C ₄ H ₉ ) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH ₃ ) ₃ COCH ₂ CH (CH ₃ ) OH (propylene glycol t-butyl ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₂ (H or (CH ₃ ) ₃ ) (dipropylene glycol t-butyl (or di-t-butyl) ether), (CH ₃ ) ₃ CO [CH ₂ CH (CH ₃ ) O] ₃ (H or (CH ₃ ) ₃ ) (tripropylene glycol t-butyl (or di-t-butyl) ether), C ₅ H ₁₁ OCH ₂ CH (CH ₃ ) OH (propylene glycol n -Pentyl ether), C ₄ H ₉ OCH ₂ CH (C ₂ H ₅ ) OH (butylene glycol n-butyl ether), C ₄ H ₉ O [CH ₂ CH (C ₂ H ₅ ) O] ₂ H (di Butylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C ₂ H ₅ C (CH ₂ O (CH ₂ ) ₃ CH ₃ ) ₃ ) and trimethylolpropane di-n-butyl ether (C ₂ H ₅ C (CH ₂ OC (CH ₂ ) ₃ CH ₃ ) ₂ CH ₂ OH).

Amide solubilizers of the invention include those represented by the formulas R ¹ C (O) NR ² R ³ and cyclo- [R ⁴ C (O) N (R ⁵ )], wherein R ¹ , R ² , R ³ and R ⁵ is independently selected from aliphatic and alicyclic hydrocarbon radicals of 1 to 12 carbon atoms, R ⁴ is selected from aliphatic hydrocarbylene radicals of 3 to 12 carbon atoms, and the molecular weight of the amide is from about 100 to about 300 atoms Unit of mass. The molecular weight of the amide is preferably from about 160 to about 250 atomic mass units. R ¹ , R ² , R ³ and R ⁵ are substituted hydrocarbon radicals, ie radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). May optionally include. R ¹ , R ² , R ³ and R ⁵ are heteroatom-substituted hydrocarbon radicals, ie atomic nitrogen (aza-), oxygen (oxa-) or sulfur (thia) in a radical chain composed of carbon atoms except nitrogen, oxygen or sulfur Radicals containing-). In general, three or less, and preferably a ratio of less than one-hydrocarbon substituents and heteroatoms is present in R ^{1 -3} for each ten carbon atoms, any such non-hydrocarbon substituents and heteroatoms present in the above-mentioned Consideration should be given when applying one molecular weight limit. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative R ¹ , R ² , R ³ and R ⁵ aliphatic and cycloaliphatic hydrocarbon radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert -Pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof. Amide solubilizing agents of the preferred embodiments above-mentioned formula cycloalkyl-one which may represent R ⁴ of a hydrocarbylene radical (CR ⁶ R ⁷⁾ _n, that is ^{- [R 4 C (O)} N (R 5)] Having the aforementioned molecular weight values, n is an integer from 3 to 5, R ⁵ is a saturated hydrocarbon radical having 1 to 12 carbon atoms, and R ⁶ and R ⁷ are (for each n) previously provided R ^{1 − And is} independently selected from the ^three definitions: cyclo-[(CR ⁶ R ⁷ ) _n C (O) N (R ⁵ )-]. In the lactams represented by the formula cyclo-[(CR ⁶ R ⁷ ) _n C (O) N (R ⁵ )-], all R ⁶ and R ⁷ are preferably hydrogen or a single saturated hydrocarbon radical in n methylene units And R ⁵ is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1- (saturated hydrocarbon radical) -5-methylpyrrolidin-2-one.

Representative amide solubilizers include 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1- Cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5- Methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidine-2 -One, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N, N-dibutylformamide and N, N-diisopropylacetamide, including but not limited to.

Ketone solubilizers of the invention include ketones represented by the formula R ¹ C (O) R ² , wherein R ¹ and R ² are independently selected from aliphatic, cycloaliphatic and aryl hydrocarbon radicals having 1 to 12 carbon atoms, The molecular weight of the ketone is about 70 to about 300 atomic mass units. R ¹ and R ² in the ketone are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of the ketone is preferably about 100 to 200 atomic mass units. R ¹ and R ² together form a linked hydrocarbylene radical and may form 5, 6 or 7 membered cyclic cyclic ketones such as cyclopentanone, cyclohexanone, and cycloheptanone. R ¹ and R ² may optionally include substituted hydrocarbon radicals, ie, radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). R ¹ and R ² are heteroatom-substituted hydrocarbon radicals, ie, atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain consisting of carbon atoms except nitrogen, oxygen, and sulfur It may optionally include a radical containing. In general, up to 3, preferably up to 1 non-hydrocarbon substituents and heteroatoms are present for every 10 carbon atoms of R ¹ and R ² , and the presence of any such non-hydrocarbon substituents and heteroatoms is Consideration should be given when applying the stated molecular weight limitations. Representative R ¹ and R ² aliphatic, cycloaliphatic and aryl hydrocarbon radicals of the formula R ¹ C (O) R ² are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso Pentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and Phenethyl.

Representative ketone solubilizing agents are 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2- Hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalon, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

The nitrile solubilizing agent of the present invention comprises a nitrile represented by the formula R ¹ CN, wherein R ¹ is selected from aliphatic, cycloaliphatic or aryl hydrocarbon radicals having 5 to 12 carbon atoms and the molecular weight of the nitrile is about 90 to about 200 Atomic mass units. R ¹ in the nitrile solubilizing agent is preferably selected from aliphatic and cycloaliphatic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of the nitrile solubilizer is preferably from about 120 to about 140 atomic mass units. R ¹ may optionally include substituted hydrocarbon radicals, ie radicals containing non-hydrocarbon substituents selected from halogen (eg fluorine, chlorine) and alkoxides (eg methoxy). R ¹ contains a heteroatom-substituted hydrocarbon radical, ie, atomic nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain composed of carbon atoms except nitrogen, oxygen, and sulfur Radicals may optionally be included. In general, up to 3, preferably up to 1 non-hydrocarbon substituent and heteroatom are present for every 10 carbon atoms of R ¹ , and the presence of any such non-hydrocarbon substituent and heteroatom Consideration should be given when applying restrictions. Representative R ¹ aliphatic, cycloaliphatic and aryl hydrocarbon radicals in formula R ¹ CN are pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and these Coordination isomers of, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizers include 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cya Nononane, 1-cyanodecane, 2-cyanodecane, 1-cyanooundecan and 1-cyanododecane.

The chlorocarbon solubilizing agent of the present invention comprises chlorocarbon represented by the formula RCl _x , wherein x is 1 or 2, R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms, and the molecular weight of the chlorocarbon Is from about 100 to about 200 atomic mass units. The molecular weight of the chlorocarbon solubilizer is preferably about 120 to 150 atomic mass units. Representative R aliphatic and cycloaliphatic hydrocarbon radicals in formula RCl _x are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, Cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and coordination isomers thereof.

Representative chlorocarbon solubilizers include 3- (chloromethyl) pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane, including but not limited to.

Ester solubilizers of the invention include esters represented by the formula R ¹ C (O) OR ² , wherein R ¹ and R ² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O and have a molecular weight of about 80 to about 550 atomic mass units.

Representative esters include (CH ₃ ) ₂ CHCH ₂ O (O) C (CH ₂ ) _2-4 (O) COCH ₂ CH (CH ₃ ) ₂ (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptano Ate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (commercial C ₇ alkyl acetates), “Exate 800” (commercial C ₈ alkyl acetates), dibutyl phthalate, and tert-butyl acetate.

Lactone solubilizers of the present invention include lactones represented by the formulas A, B, and C below.

These lactones contain the functional group -C (O) O- in the 6-membered ring A, or preferably in the 5-membered ring B, and for formulas A and B, R ₁ to R ₈ are hydrogen or linear, branched And cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R ₁ to R ₈ may be linked to another R ₁ to R ₈ to form a ring. The lactones may have exocyclic alkylidene groups as in Formula C, wherein R ₁ to R ₆ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals . Each R ₁ to R ₆ may be linked to another R ₁ to R ₆ to form a ring. The molecular weight of the lactone solubilizer is about 80 to about 300 atomic mass units, preferably about 80 to about 200 atomic mass units.

Representative lactone solubilizers include, but are not limited to, the compounds listed in Tables 4A-4C.

The kinematic viscosity of the lactone solubilizer is generally less than about 7 centistokes at 40 ° C. For example, the kinematic viscosity of gamma-undecalactone at 40 ° C. is 5.4 centistokes and the viscosity of cis- (3-hexyl-5-methyl) dihydrofuran-2-one is 4.5 centistokes. Lactone solubilizers are commercially available or may be prepared by methods as described in US Patent Application No. 10 / 910,495, filed August 3, 2004, which is incorporated herein by reference.

The aryl ether solubilizer of the present invention includes an aryl ether represented by the formula R ¹ OR ² , wherein R ¹ is selected from aryl hydrocarbon radicals having 6 to 12 carbon atoms, and R ² is an aliphatic hydrocarbon radical having 1 to 4 carbon atoms. And the molecular weight of the aryl ether is from about 100 to about 150 atomic mass units. Representative R ¹ aryl radicals of the formula R ¹ OR ² include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R ² aliphatic hydrocarbon radicals in formula R ¹ OR ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether solubilizers include, but are not limited to, methyl phenyl ether (anisole), 1,3-dimethoxybenzene, ethyl phenyl ether and butyl phenyl ether.

Fluoroether solubilizing agents of the invention include those represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ¹ is an aliphatic, cycloaliphatic, and aromatic hydrocarbon radical, preferably primary, having from about 5 to about 15 carbon atoms Selected from linear saturated alkyl radicals. Representative fluoroether solubilizers include, but are not limited to, C ₈ H ₁₇ OCF ₂ CF ₂ H and C ₆ H ₁₃ OCF ₂ CF ₂ H. It should be noted that when the refrigerant is a fluoroether, the solubilizer may not be the same fluoroether.

The fluoroether solubilizer may further comprise ethers derived from fluoro-olefins and polyols. The fluoro-olefin may be of the form CF ₂ = CXY, where X is hydrogen, chlorine or fluorine, Y is chlorine, fluorine, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ , or C ₃ F ₇ . Representative fluoro-olefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyols may be linear or branched. The linear polyol may be of the type HOCH ₂ (CHOH) _x (CRR ′) _y CH ₂ OH, where R and R ′ are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer from 0 to 4, y is 0 It is an integer of -4. Branched polyols are of the form C (OH) _t (R) _u (CH ₂ OH) _v [(CH ₂ ) _m CH ₂ OH] _w where R is hydrogen, CH ₃ or C ₂ H ₅ , and m is 0 Is an integer of 3 to 3 and t and u are 0 or 1, v and w are integers of 0 to 4, and here t + u + v + w = 4. Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.

The 1,1,1-trifluoroalkane solubilizer of the present invention comprises 1,1,1-trifluoroalkane represented by the formula CF ₃ R ¹ , wherein R ¹ is an aliphatic having from about 5 to about 15 carbon atoms And cycloaliphatic hydrocarbon radicals, preferably primary linear saturated alkyl radicals. Representative 1,1,1-trifluoroalkane solubilizers include, but are not limited to, 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

The solubilizers of the present invention may be present as a single compound or as a mixture of one or more solubilizers. The mixture of solubilizers may contain two solubilizers from the same class of compounds, for example two lactones, or two solubilizers from two different classes, such as lactones and polyoxyalkylene glycol ethers. Can be.

In the compositions of the present invention comprising a refrigerant and a UV fluorescent dye or comprising a heat transfer fluid and a UV fluorescent dye, the UV dye is from about 0.001% to about 1.0% by weight of the composition, preferably from about 0.005% to about 0.5 Wt%, most preferably 0.01 wt% to about 0.25 wt%.

The solubility of these UV fluorescent dyes in refrigerants and heat transfer fluids can be poor. Thus, methods for introducing these dyes into refrigeration or air conditioning apparatus are difficult, costly and time consuming. U.S. Patent No. RE 36,951 describes a method using dye powders, solid pellets or slurries of dyes that can be inserted as components of a refrigeration or air conditioning apparatus. As the refrigerant and lubricant circulate through the device, the dye is dissolved or dispersed and transported throughout the device. Numerous other methods for introducing dyes into refrigeration or air conditioning apparatus are described in the literature.

Ideally, UV fluorescent dyes can be dissolved in the refrigerant itself and do not require special methods for introduction into refrigeration or air conditioning apparatus. The present invention relates to a composition comprising a UV fluorescent dye that can be introduced into the system in a refrigerant. The composition of the present invention will be able to store and deliver the dye-containing refrigerant and heat transfer fluid at low temperatures while maintaining the dye in solution.

In a composition of the present invention comprising a refrigerant, a UV fluorescent dye and a solubilizer, or comprising a heat transfer fluid, a UV fluorescent dye and a solubilizer, the solubilizer in the refrigerant or heat transfer fluid may be from about 1 to about 50 of the blended composition. Weight percent, preferably about 2 to about 25 weight percent, most preferably about 5 to about 15 weight percent. In the compositions of the present invention, the UV fluorescent dye is from about 0.001% to about 1.0% by weight, preferably from 0.005% to about 0.5% by weight, most preferably from 0.01% to about 0.25% by weight in the refrigerant or heat transfer fluid. It is present at a concentration of

Optionally, refrigeration or air conditioning system additives commonly used to enhance performance and system stability can be added to the compositions of the present invention as needed. These additives are known in the field of refrigeration and air conditioning and include, but are not limited to, antiwear agents, extreme pressure lubricants, corrosion and antioxidants, metal surface deactivators, free radical scavengers, and foam control agents. . In general, these additives are present in the compositions of the present invention in small amounts relative to the total composition. Typically, each additive is used at a concentration of less than about 0.1 weight percent to about 3 weight percent. These additives are selected based on the individual system requirements. These additives are triaryl phosphate-based EP (extreme) lubricating additives, such as butylated triphenyl phosphate (BTPP), or other alkylated triaryl phosphate esters, such as Syn-O-Ad 8478 (Akzo Chemicals )), Tricresyl phosphate and related compounds. In addition, metal dialkyl dithiophosphates (eg, zinc dialkyl dithiophosphates (or ZDDPs), Lubrizol 1375 and other materials of this compound family may be used in the compositions of the present invention. Prophylactic additives include natural product oils, and asymmetric polyhydroxyl lubricating additives such as Syngolgol TMS (International Lubricants) Similarly, antioxidants, free radical scavengers, and water Stabilizers such as scavengers can be used This class of compounds may include, but is not limited to, butylated hydroxy toluene (BHT) and epoxides.

Solubilizers such as ketones can have an unpleasant odor, which can be blocked by the addition of odor masking agents or fragrances. Common examples of odor masks or fragrances include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel. As well as d-limonene and pinene. Such malodor masking agents may be used in concentrations of about 0.001% to about 15% by weight, based on the combined weight of the malodor masking agent and the solubilizing agent.

The present invention further relates to a method of using a refrigerant or heat transfer fluid composition further comprising an ultraviolet fluorescent dye, and optionally a solubilizer, in a refrigeration or air conditioning apparatus. Such methods include introducing a refrigerant or heat transfer fluid composition into a refrigeration or air conditioning device. This can be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizer and introducing the blend into the device. Alternatively, this can be done by combining the solubilizer and the UV fluorescent dye and introducing the blend into a refrigeration or air conditioning apparatus that stores the refrigerant and / or heat transfer fluid. The resulting composition can be used in refrigeration or air conditioning apparatus.

Further, the present invention relates to a method of detecting leaks using a refrigerant or heat transfer fluid composition comprising an ultraviolet fluorescent dye. The presence of dyes in the composition makes it possible to detect leaks of refrigerant in refrigeration or air conditioning devices. Leak detection helps to solve or prevent inefficient operation of the device or system or equipment failure. Leak detection also helps the user to contain the compounds used to operate the device.

This method provides a refrigeration and air conditioning apparatus comprising a refrigerant and an ultraviolet fluorescent dye or comprising a heat transfer fluid and a UV fluorescent dye as described herein, and optionally a solubilizer as described herein and detecting a UV fluorescent dye containing refrigerant. And using suitable means to do so. Suitable means for detecting dyes include, but are not limited to, ultraviolet lamps, often referred to as "black light" or "blue light". Ultraviolet lamps designed specifically for this purpose are available from numerous sources. After introducing a composition containing an ultraviolet fluorescent dye into a refrigeration or air conditioning apparatus and circulating throughout the system, the leak can be found by observing the fluorescence of the dye near any leak point by illuminating the ultraviolet lamp on the apparatus.

Further, the present invention relates to a method for producing cooling or heat using the composition of the present invention, which method is intended to cool or heat by evaporating the composition in the vicinity of the object to be cooled and then condensing the composition. Condensing the composition in the vicinity of an object to produce heat by evaporating the composition. When the composition of the present invention comprises a refrigerant or heat transfer fluid composition with an ultraviolet fluorescent dye, and / or a solubilizer, the refrigerant or heat transfer fluid component of the composition is evaporated and then condensed to cool, or condensed and then evaporated. To generate heat.

Mechanical refrigeration is primarily an application of thermodynamics in which a cooling medium, such as a refrigerant, is circulated so that it can be recovered for reuse. Commonly used circulation includes steam-compression, absorption, steam-jet or steam-ejector and air.

The vapor compression refrigeration system includes an evaporator, a compressor, a condenser, and an expansion device. The vapor compression cycle reuses the refrigerant in multiple stages, creating a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. The liquid refrigerant is introduced into the evaporator through the expansion device, and the liquid refrigerant boils in the evaporator at low temperatures to form gas and cause cooling. Low pressure gas is introduced into the compressor where the gas is compressed and the pressure and temperature are increased. Thereafter, a higher pressure (compressed) gaseous refrigerant is introduced into the condenser where the refrigerant condenses and discharges its heat to the surroundings. The refrigerant is returned to the expansion device whereby the liquid expands from the higher pressure level in the condenser to the lower pressure level in the evaporator and repeats the cycle.

The present invention further relates to a cooling method comprising evaporating the composition of the invention in the vicinity of an object to be cooled and then condensing said composition.

Further, the present invention relates to a method for generating heat, comprising condensing the composition of the invention in the vicinity of the object to be heated and then evaporating the composition.

There are various types of compressors that can be used for refrigeration applications. The compressor may be reciprocating, rotating, jetting, centrifugal, scrolling, screwing or axial-flow, or for the fluid being compressed, depending on the mechanical means for compressing the fluid. Depending on the way the mechanical member acts, it can generally be classified as positive displacement (eg reciprocating, scrolling or screwing) or dynamic (eg centrifugal or jetting). .

A bi-displacement or dynamic compressor can be used in the method of the present invention. Centrifugal compressors are preferred apparatus for the refrigerant composition of the present invention.

Centrifugal compressors use a rotating member that radially accelerates the refrigerant and typically includes an impeller and a diffuser housed in the casing. Centrifugal compressors usually take fluid at the impeller eye or at the central inlet of the circulating impeller and accelerate it radially outward. A slight increase in static pressure occurs in the impeller, but most of the pressure rise occurs in the diffuser zone of the casing, where the speed is converted to constant pressure. Each impeller-diffuser set is one stage of the compressor. Centrifugal compressors consist of one to twelve stages or more, depending on the final pressure desired and the volume of refrigerant to be handled.

The pressure ratio, or compression ratio, of the compressor is the ratio of absolute discharge pressure to absolute injection pressure. The pressure delivered by the centrifugal compressor is substantially constant over a relatively wide range of capacities.

A bi-displacement compressor draws steam into the chamber and compresses the steam by reducing the volume of the chamber. After compression, the vapor is forced out of the chamber by further reducing the chamber volume to zero or nearly zero. Pressure can be built up in a bi-displacement compressor, which is limited only by the strength and volumetric efficiency of the components that withstand the pressure.

Unlike bi-displacement compressors, centrifugal compressors compress the steam passing through the impeller entirely dependent on the centrifugal force of the high speed impeller. It is therefore referred to as a dynamic compressor, not bi-displacement.

The pressure at which the centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at the tip of the impeller and is related to the diameter of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the path through the impeller. For this reason, the size of the compressor is more dependent on the required pressure than on the capacity.

Because centrifugal compressors operate at high speeds, they are essentially high pressure low pressure equipment. Centrifugal compressors work best when using low pressure refrigerants such as trichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane (CFC-113).

Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors are designed for high speeds of about 40,000 to about 70,000 rpm and typically have a small impeller size of less than 0.15 meters (about 6 inches).

By using a multistage impeller in a centrifugal compressor to improve compressor efficiency, less force is required in use. In a two-stage system, in operation the exhaust of the first stage impeller enters the suction of the second impeller. Both impellers can be operated using a single shaft (or shaft). Each stage may have a compression ratio of about 4 to 1 (ie, the absolute discharge pressure may be four times the absolute suction pressure). In particular for automotive applications, several examples of two-stage centrifugal compressor systems are described in US Pat. Nos. 5,065,990 and 5,363,674, which are incorporated herein by reference.

Compositions of the present invention suitable for use in refrigeration or air conditioning systems using centrifugal compressors include C ₄ F ₉ OCH ₃ and

N- (difluoromethyl) -N, N-dimethylamine,

Diisopropyl ether,

Dimethoxymethane,

Ethyl acetate,

Ethyl formate,

Methanol,

Methyl acetate,

Methyl formate,

tert-butyl methyl ether,

Trans-1,2-dichloroethylene, and

C ₄ F ₉ OC ₂ H ₅ and trans-1,2-dichloroethylene

At least one compound selected from the group consisting of.

In addition, the compositions listed above are suitable for use in multistage centrifugal compressors, preferably two-stage centrifugal compressor apparatus.

The compositions of the present invention can be used in stationary air conditioning, heat pumps or mobile air conditioning and refrigeration systems. Stationary air conditioning and heat pump applications serve commercial applications including windowed, ductless, ducted, packaged terminals, quenchers, and packaged rooftops. Include. Refrigeration applications include refrigerators and freezers for home or house, ice makers, self-contained coolers and freezers, walk-in coolers and freezer and transport refrigeration systems.

The compositions of the present invention can additionally be used in air conditioning, heating and refrigeration systems using fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single channel tube or plate heat exchangers.

Typical microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention. Low operating pressures and densities result in high flow rates and high friction losses in all components. In such cases, the evaporator design may be modified. A single slab / single channel heat exchanger arrangement may be used rather than several microchannel slabs connected in series (for the refrigerant path). Thus, the preferred heat exchanger for low pressure refrigerants of the present invention is a single slab / single passage heat exchanger.

In addition to two-stage or other multi-stage centrifugal compressor devices, the compositions of the present invention suitable for use in refrigeration or air conditioning devices using a single slab / single channel heat exchanger include C ₄ F ₉ OCH ₃ and

N- (difluoromethyl) -N, N-dimethylamine,

Diisopropyl ether,

Dimethoxymethane,

Ethyl acetate,

Ethyl formate,

Methanol,

Methyl acetate,

Methyl formate,

tert-butyl methyl ether,

Trans-1,2-dichloroethylene, and

C ₄ F ₉ OC ₂ H ₅ and trans-1,2-dichloroethylene

At least one compound selected from the group consisting of.

The compositions of the present invention are particularly useful for small turbine centrifugal compressors (mini centrifugal compressors), which can be used in automotive and windowed air conditioning, heat pumps or transport refrigeration as well as other applications. These high efficiency mini centrifugal compressors can be driven by an electric motor and thus can operate independently of engine speed. Constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This offers the potential for improved efficiency, especially at higher engine speeds, compared to typical R-134a automotive air conditioning systems. Given the cyclical operation of a typical system at high drive speeds, the benefits of these low pressure systems will be even greater.

Alternatively, the mini centrifugal compressor can be driven by an engine exhaust gas driven turbine or an assembly of proportional belt drives and proportional gear drives rather than using power. Current power used in automotive designs is about 14 volts, but the new mini centrifugal compressors require about 50 volts. Thus, the use of alternative power sources would be advantageous. Refrigeration or air conditioning apparatus driven by an engine exhaust gas driven turbine is described in detail in US Provisional Application No. 60 / 658,915, filed March 4, 2005, which is incorporated herein by reference. Refrigeration or air conditioning devices driven by proportional gear drive assemblies are described in US Provisional Application No. 60/663924, filed March 21, 2005, which is incorporated herein by reference.

Further, the present invention provides a cooling comprising compressing the composition of the invention in a mini centrifugal compressor driven by an engine exhaust gas driven turbine, condensing the composition and then evaporating the composition in the vicinity of the object to be cooled. It is about a method.

Further, the present invention compresses the composition of the present invention in a mini centrifugal compressor driven by a proportional belt drive and a proportional gear drive assembly, condenses the composition, and then evaporates the composition in the vicinity of the object to be cooled. It relates to a cooling method comprising the step of.

Some low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal apparatus.

Additionally, the present invention relates to a method for replacing CFC-113 in an existing refrigeration apparatus or air conditioning apparatus, which method comprises providing a composition of the present invention as a substitute.

In addition, the present invention relates to a method of transferring heat from a heat source to a heat sink, wherein the composition of the present invention acts as a heat transfer fluid. The method for heat transfer includes transferring the composition of the present invention from a heat source to a heat sink.

Heat transfer fluids are used to transfer, move or remove heat from one space, place, object or object to another space, place, object or object by radiation, conduction, or convection. The heat transfer fluid may function as a secondary refrigerant by providing a means for transferring heat for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain constant (ie, not evaporate or condense) throughout the transfer process. Alternatively, the evaporative cooling process can also utilize heat transfer fluids.

The heat source may be defined as any space, place, object or object for which it is desirable to transfer, move or remove heat. Examples of heat sources may be (open or closed) spaces that require refrigeration or cooling, such as refrigerators or freezer cases in supermarkets, building spaces that require air conditioning, or cabins of automobiles that require air conditioning. The heat sink may be defined as any space, place, object or object capable of absorbing heat. The vapor compression refrigeration system is an example of such a heat sink.

Example 1

Impact of Vapor Leakage

At a certain temperature the initial composition was filled into a container and the initial vapor pressure of the composition was measured. The composition was leaked from the container while 50% by weight of the initial composition was removed while maintaining the temperature constant, and the vapor pressure of the composition remaining in the container was measured when 50% by weight of the initial composition was removed. The results are summarized in Tables 5a-5d below.

The results indicate that the vapor pressure difference between the original composition and the composition remaining after 50% by weight is removed is less than about 10% for the composition of the present invention. This indicates that the composition of the present invention is azeotropic or near-azeotropic.

Example  2

Tip speed to generate pressure

Tip speed can be estimated by establishing some basic relationships for refrigeration units using centrifugal compressors. The torque that the impeller ideally imparts to the body is defined by the following equation.

In the above formula,

T is the torque (N * m),

m is the mass flow rate (kg / s),

v ₂ is the tangential velocity (tip velocity) of the refrigerant leaving the impeller (m / s),

r ₂ is the radius (m) of the impeller exit,

v ₁ is the tangential velocity (m / s) of the refrigerant introduced into the impeller,

r ₁ is the radius (m) of the impeller inlet.

Assuming that the refrigerant is introduced into the impeller essentially in the axial direction, the tangential component v ₁ of velocity is zero, so that Equation 2 is established.

The power required at the shaft is the product of torque and rotational speed.

In the above formula,

P is power (W),

w is the rotational speed in radians / s,

Therefore, the following equation (4) is established.

At low refrigerant flow rates, the tip velocity of the impeller and the tangential velocity of the refrigerant are about the same. Accordingly, the following equations 5 and 6 are established.

Another representation of the ideal power is the product of the mass flow rate and the isentropic work of compression.

In the above formula,

H _i is the difference in enthalpy (kJ / kg) between saturated vapor in evaporation and refrigerant in saturated condensation.

Combining Equations 6 and 7 establishes Equation 8 below.

Equation 8 is based on some basic assumptions, but this provides a good estimate of the tip speed of the impeller and provides an important way of comparing the tip speeds of the refrigerant.

Table 6 below shows the theoretical tip rates calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and 3-ethylpentane of the present invention. The conditions assumed for this comparison are:

Evaporator temperature 40.0 ° F (4.4 ° C),

Condenser temperature 110.0 ° F (43.3 ° C),

Liquid subcool temperature 10.0 ° F (5.5 ° C),

Return gas temperature 75.0 ° F. (23.8 ° C.),

Compressor efficiency is 70%.

These are typical conditions under which small turbine centrifugal compressors are carried out.

This example shows that the compounds of the present invention have a tip speed within about +/- 30% of CFC-113 and are effective CFC-113 replacements with minimal compressor design changes. The tip speed of the most preferred composition is within about +/- 15% of CFC-113.

Example 3

Performance data

Table 7 below shows the performance of various refrigerants compared to CFC-113. Data was based on the following conditions.

Evaporator temperature 40.0 ° F (4.4 ° C),

Condenser temperature 110.0 ° F (43.3 ° C),

Subcool temperature 10.0 ° F (5.5 ° C),

Return gas temperature 75.0 ° F. (23.8 ° C.),

Compressor Efficiency 70%

The data indicate that the compositions of the present invention have evaporator and condenser pressures similar to CFC-113. In addition, some compositions had higher capacity or energy efficiency than CFC-113.

Claims (23)

C ₄ F ₉ OCH ₃ and N- (difluoromethyl) -N, N-dimethylamine, Diisopropyl ether, Dimethoxymethane, Ethyl acetate, Ethyl formate, Methanol, Methyl acetate, Methyl formate, tert-butyl methyl ether, Trans-1,2-dichloroethylene, and C ₄ F ₉ OC ₂ H ₅ and trans-1,2-dichloroethylene A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of: C ₄ F ₉ OCH ₃ and suitable for use in (i) centrifugal compressors, or (ii) multi-stage centrifugal compressors, or (iii) refrigeration or air conditioning apparatus using a single slab / single channel heat exchanger. N- (difluoromethyl) -N, N-dimethylamine, Diisopropyl ether, Dimethoxymethane, Ethyl acetate, Ethyl formate, Methanol, Methyl acetate, Methyl formate, tert-butyl methyl ether, Trans-1,2-dichloroethylene, and C ₄ F ₉ OC ₂ H ₅ and trans-1,2-dichloroethylene A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of: About 1 to about 99 weight percent C ₄ F ₉ OCH ₃ and about 99 to about 1 weight percent N- (difluoromethyl) -N, N-dimethylamine, About 1 to about 84 weight percent C ₄ F ₉ OCH ₃ and about 99 to about 16 weight percent dimethoxymethane, About 58 to about 99 weight% C ₄ F ₉ OCH ₃ and about 42 to about 1 weight% ethyl acetate, About 46 to about 86 weight percent C ₄ F ₉ OCH ₃ and about 54 to about 14 weight percent ethyl formate, About 49 to about 87 weight percent C ₄ F ₉ OCH ₃ and about 51 to about 13 weight percent methyl acetate, About 37 to about 83 weight percent C ₄ F ₉ OCH ₃ and about 63 to about 17 weight percent methyl formate, or About 10 to about 70 weight percent C ₄ F ₉ OCH ₃ , about 5 to about 60 weight percent C ₄ F ₉ OC ₂ H ₅ , and about 25 to about 80 weight percent trans-1,2-dichloroethylene Azeotropic or near-azeotropic compositions comprising a. 41.1 wt% C ₄ F ₉ OCH ₃ and 58.9 wt% N- (difluoromethyl) -N, N-dimethylamine having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.5 ° C., 56.3 wt% C ₄ F ₉ OCH ₃ and 43.7 wt% dimethoxymethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 42.0 ° C., 87.8 wt% C ₄ F ₉ OCH ₃ and 12.2 wt% ethyl acetate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 57.9 ° C., 68.6 wt% C ₄ F ₉ OCH ₃ and 31.4 wt% ethyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 41.0 ° C., 72.1 wt% C ₄ F ₉ OCH ₃ and 27.9 wt% methyl acetate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 42.5 ° C., or 57.4 wt% C ₄ F ₉ OCH ₃ and 42.6 wt% methyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 26.0 ° C. Azeotropic composition comprising a. A method according to claim 1, comprising evaporating the composition of claim 1 in the vicinity of the object to be cooled, and then condensing said composition. A method for generating heat, comprising evaporating the composition after condensing the composition of claim 1 in the vicinity of the object to be heated. A method of using the composition for heat transfer comprising transferring the composition according to any one of claims 1 to 4 from a heat source to a heat sink. The at least one ultraviolet light according to claim 1, which is selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. A composition further comprising a fluorescent dye. The method of claim 8, wherein the hydrocarbon, dimethyl ether, polyoxyalkylene glycol ether, amide, ketone, nitrile, chlorocarbon, ester, lactone, aryl ether, hydrofluoroether, and 1,1,1-trifluoroalkane The composition further comprises at least one solubilizer selected from the group consisting of, wherein the refrigerant or heat transfer fluid may not be the same compound as the solubilizer. The method of claim 9 wherein the solubilizer is a) a polyoxyalkylene glycol ether having a molecular weight of about 100 to about 300 atomic mass units and represented by the formula R ¹ [(OR ² ) _x OR ³ ] _y , where x is an integer from 1 to 3 and y is from 1 to Is an integer of 4, R ¹ is selected from hydrogen and an aliphatic hydrocarbon radical having 1 to 6 carbon atoms and having y bond sites, R ² is selected from an aliphatic hydrocarbylene radical having 2 to 4 carbon atoms, R ³ Silver is selected from hydrogen and aliphatic and cycloaliphatic hydrocarbon radicals having 1 to 6 carbon atoms, and at least one of R ¹ and R ³ is selected from said hydrocarbon radicals), b) amides having a molecular weight of about 100 to about 300 atomic mass units and represented by the formula R ¹ CONR ² R ³ and cyclo- [R ⁴ CON (R ⁵ )-], wherein R ¹ , R ² , R ³ and R ⁵ Is independently selected from aliphatic and cycloaliphatic hydrocarbon radicals of 1 to 12 carbon atoms, and up to 1 aromatic radical of 6 to 12 carbon atoms, and R ⁴ is selected from aliphatic hydrocarbylene radicals of 3 to 12 carbon atoms) , c) ketones having a molecular weight of about 70 to about 300 atomic mass units and represented by the formula R ¹ COR ² , wherein R ¹ and R ² are independently selected from aliphatic, cycloaliphatic and aryl hydrocarbon radicals having 1 to 12 carbon atoms, d) a nitrile having a molecular weight of about 90 to about 200 atomic mass units and represented by the formula R ¹ CN, wherein R ¹ is selected from aliphatic, cycloaliphatic or aryl hydrocarbon radicals having 5 to 12 carbon atoms, e) chlorocarbons having a molecular weight of about 100 to about 200 atomic mass units represented _{by the} formula RCl _x , wherein x is 1 or 2 and R is selected from aliphatic and cycloaliphatic hydrocarbon radicals having 1 to 12 carbon atoms, f) aryl ethers having a molecular weight of about 100 to about 150 atomic mass units represented by the formula R ¹ OR ² , wherein R ¹ is selected from aryl hydrocarbon radicals having 6 to 12 carbon atoms, and R ² has 1 to 4 carbon atoms Aliphatic hydrocarbon radicals), g) 1,1,1-trifluoroalkane represented by the formula CF ₃ R ¹ , wherein R ¹ is selected from aliphatic and cycloaliphatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, h) a fluoroether represented by the formula R ¹ OCF ₂ CF ₂ H, wherein R ¹ is selected from aliphatic and cycloaliphatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, or the fluoroether is selected from the group consisting of fluoro-olefins and Derived from a polyol, wherein the fluoro-olefin is of the form CF ₂ = CXY, where X is hydrogen, chlorine or fluorine, Y is chlorine, fluorine, CF ₃ or OR _f , where R _f is CF ₃ , C ₂ F ₅ , or C ₃ F ₇ , wherein the polyol is linear or branched, and the linear polyol may be of the type HOCH ₂ (CHOH) _x (CRR ′) _y CH ₂ OH, wherein R and R ′ are hydrogen, CH ₃ or C ₂ H ₅ , x is an integer from 0 to 4, y is an integer from 0 to 3 and z is 0 or 1 and the branched polyol is C (OH) _t (R) _u (CH ₂ OH ) _v [(CH ₂ ) _m CH ₂ OH] _w , wherein R is hydrogen, CH ₃ or C ₂ H ₅ , m is an integer from 0 to 3 and t and u are 0 or 1, v and w Is 0 It is an integer of not 4, and Im wherein t + u + v + w = 4), i) a lactone having a molecular weight of about 100 to about 300 atomic mass units represented by the following formulas B, C, and D, and j) esters having a molecular weight of about 80 to about 550 atomic mass units and represented by the formula R ¹ CO ₂ R ² , wherein R ¹ and R ² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; Composition selected from the group consisting of. <Formula B>

<Formula C>

<Formula D>

(R ¹ to R ⁸ are independently selected from hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals) Apparatus for compression freezing or air conditioning an ultraviolet fluorescent dye comprising dissolving the ultraviolet fluorescent dye in the composition of any one of claims 1 to 4 in the presence of a solubilizer and introducing the formulation into the compression freezing or air conditioning apparatus. How to Introduce A method of dissolving an ultraviolet fluorescent dye in said composition comprising contacting the composition of any one of claims 1 to 4 with an ultraviolet fluorescent dye in the presence of a solubilizer. Providing a compressed refrigeration apparatus or an air conditioning apparatus, incorporating the composition of claim 8 or 9 into the apparatus, and providing a suitable means for detecting the composition in the vicinity of the apparatus. Way. A method of cooling comprising evaporating the refrigerant or heat transfer fluid component of the composition of claim 8 in the vicinity of an object to be cooled. Condensing the refrigerant or heat transfer fluid component of the composition of claim 8 in the vicinity of the object to be heated, and then evaporating said refrigerant or heat transfer fluid component. The composition of claim 1 further comprising a stabilizer, a water scavenger, or a malodor masking agent. The composition of claim 16 wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones. A method of using the composition of any one of claims 1 to 4 comprising producing cooling or heat in a refrigeration or air conditioning apparatus using a multistage centrifugal compressor. 19. The method of claim 18, wherein the multistage centrifugal compressor is a two stage centrifugal compressor. The composition of claim 16 wherein said water scavenger is an ortho ester. Compressing the composition of claim 1 in a mini centrifugal compressor driven by an engine exhaust gas driven turbine, condensing the composition and then evaporating the composition in the vicinity of the object to be cooled. Cooling method. A mini centrifugal compressor driven by an assembly of a proportional belt drive and a proportional gear drive compresses the composition of any one of claims 1 to 4, condenses the composition, and then A cooling method comprising evaporating in the vicinity. A method for replacing CFC-113 in an existing refrigeration or air conditioning apparatus, comprising as an alternative, providing the composition of any one of claims 1-4.